Polymerization products of nu-(2-pyridyl)-beta-cyano acrylic amides



United States PatentO POLYMERIZATION PRODUCTS OF 'N-(2-PYRIDYL)-BETA-CYANO ACRYLIC AMIDES Gaetano F. DAlelio, Pittsburgh, Pa., assignorto Kopp'ers Company, Inc., a corporation of Delaware v No Drawing.Application August 31, 1951-,

Serial No. 244,706

27 Claims. erase-ass ence or absence of other mono-ethyleniccopolymerizable compounds especially acrylonitrile. The invention alsorelates to compositions of these polymerization products adapted to theformation of shaped articles, in many cases to molecularly orientedshaped articles, particularly to fibers, threads, bristles,mono-filaments, etc., hereinafter referred to as fibers, and othershaped articles such as films and the like, which articles show improveddyeing properties.

It has been known for some time that certain copolymers of acrylonitrilemay be adapted to thepreparation of shaped articles, such as films,fibers, foils, tubes, etc. Some of these copolymers have been regardedas capable of being cold-drawn to produce structures molecularlyoriented along the fiber axis. Cold-drawing may be defined as thestretchingof a polymeric material at a temperature below the meltingpoint of the material to give a molecularly oriented structure.

The resistance of acrylonitrile polymersfto dyes of all types haspresented serious dyeing problems, especially in the development ofsynthetic fibers from these polymers. In fact, in order to dyepolyaerylonitrile one commercial process resorts to the use of highpressures with water solutions or organic dispersions'of dyes. It hasbeen proposed that improvement in dye susceptibihty can be obtained bythe use of itaconic acid in sm 1 amounts as copolymerizing monomer inthe preparation of acrylonitrile polymers. However, the polymer productsobtained thereby have a tendency'totcrosslink noon standing attemperatures of at least about 570 8.0 C. or upon spinning from hotsolutions. .Snch cross linking causes spoliation of materialbygelation'during storage, embrittlement of fibers, fouling of spinningjets, and other production difficulties.- i

In accordance with the present inventionwit'has now been found thatimprovements in dyeing properties ofr acrylonitrile polymers areobtained by the polymerization of polymen'zable massescomprising-acrylonitrile and a pyridyl amide of beta-cyano-acr-ylic acidor betacyano-mcthacrylic acid, with or without other copolymerizableethylenic compounds. ther that in addition to the fact that the pyridylamides of beta-cyano-acrylic acid and 'beta-cyano-inethacrylic acidyield particularly valuable copolymers with acrylonitrile, they may alsobe used efiectively to form ca polymers with other types ofeopolymer'izable ethylen'ic compounds having a CH2==C group. Thus it hasbeen found that valuable polymerization products may be prepared inaccordance with the invention by polymerizing a mass comprising apyridyl amide of a beta cyanoacrylic or beta-cyano-methacrylic acid inthe presence of one or more other ethylen'ic compounds listedhereinafter.

It has been found fun The pyridyl amides of-ibeta cyanmacrylic or:

2,703,317 Patented Mar. 1, 1955 cyano-methacrylic used in the practiceof the invention may be represented by the general formulaCN-CH=CR--CO--NR'-P in which R is hydrogen or the methyl group, R isselected from the class eonsisting'of hydrogen and alkyl groups, suchas, methyl, ethyl, isopropyl, n-butyl, secbutyl, amyl, hexyl, decyl, andthe like, preferably containing less than four carbon atoms and P is apyridine nucleus. unsubstituted. substituents be a hydrocarbon group orgroups containing not more than a total of five carbon atoms as in the.case of the monoethyl pyridines, the dimethyl pyridines, the diethylpyridines, the methyl ethyl pyridines, isoquinoline, quinoline, and thealkylated quinolines such as quinaldine.

The N-pyridyl be-ta-cyano-acrylamides are readily prepared by reactingthe amino pyridines with beta-cyanoacrylic anhydride or chloride. Forexample, N-(2- pyridyl)-beta-cyano-acrylamide can be readily prepared byreacting beta-cyano-acrylic chloride with 2-amino pyridine. Thecorresponding beta-cyano-methacrylamide is prepared by usingbeta-cyano-methacrylic an hydride or beta-cyano-methacrylic chlorideinstead of beta-cyano-acrylic anhydride or beta-cyano-acrylic chloride.Other pyridyl amides of beta-cyano-acrylic or beta-cyano-methacrylicacid may be formed in a like manner.

The proportions of the amide in the polymerization products of theinvention may vary over a wide range, ranging from equimolar proportionsof amide down to very small amounts of amide such as may be employed inacrylonitrile polymers to impart dye susceptibility thereto. Althougheven smaller amounts are somewhat effective, the improvement insusceptibility of acrylonitrile copolymers to dyes becomes particularlynoticeable when the amide content of the copolymer is about 0.1 per centand the susceptibility increases as the amount of amide is increased.Ordinarily sufiicient improvement in dye susceptibility is obtained withamounts of amide ranging up to about 10 or 15 per cent but it may beadvantageous for reasons such as in the preparation of ion-exchangepolymers or additives to improve dyeing properties to have a largerproportion of amide in the acrylonitrile copolymer. In such cases theconcentration of amide may range up to or approaching 50 mole per cent.Within these proportions acrylonitrile copolymers of the invention showgreat aflinity toward many dyes especially acidic and vat dyes.

In addition to the improvements effected in the resulting copolymers,the use of pyridyl amides of betacyano-acrylic orbeta-cya'no-methacrylic acid has certain other advantages over the useof the corresponding acids; For example, the amides are more soluble inacrylonitrile than the acids. Therefore, it is generally easier to getcomplete copolymerization of the amide with acrylonitrile in solution,emulsion and suspension polymerizations.

The acrylonitrile copolymers discussed herein are soluble inN,N-dimethyl acetamide- (DMA), N, N-dimethyl formamide- (DMF), butyrolactone, ethylene carbonate,

N,N-dimethyl methyl urethane of the formula cunzNcooc'ns ethylenecarbamate, N-tnethyl-Z-pyrrolidone, 'and lja number of similar solvents,used alone or in conjunction with N,N-d1rnethyl cyanamide, N,N-dimethylcyano-acetamide, N,N dimethyl methoxy acetamide,

- used in preparing-suchcopolymers do not have sub- The pyridine nucleusmay be substituted or If substituted, it is preferred that the .theinvention. specification, parts and percentages are lntended to meanparts by weight and percentages by weight.

Example I Five polymers of acrylonitrile are prepared from the followingmonomer compositions:

To 900 parts of water, adjusted to a pH of about three, in a suitablereactor, is added 1.0 part of am monium persulfate, 0.5 part of sodiumbisulfite, and 100 parts of monomer or monomer mixture. The reactor 1sthen flushed with deoxygenated nitrogen and heated with agitation to 50C. for 24 hours. Steam is introduced into the reactor to removeunpolymerized monomers from the mixture. A small amount of aluminumsulfate is added to the mixture and the polymer isolated by filtration.

The polymer is then washed with water and with methyl alcohol. A portionof the polymer is dissolved in dimethyl formamide, ethylene carbonate,or butyrolactone and a film cast from the solution. The film is washedentirely free of solvent and stretched at a ratio of about 8:1 in aglycerine bath at 135 to 145 C The film is then washed in water and dyedin a bath containing for each part of film 0.05 part of l,5-diamino-4,8-dihydroxy-anthraquinone-3-sulfonic acid, 003 part sulfuric acid and 50parts water (50:1 bath-film ratio) at boiling temperature for one hour.The film is then removed and washed with water and scoured for minutesin a 0.4 per cent soap solution at 85 C. Whereas the unmodifiedpolyacrylonitrile has little or no color, all of the copolymers are dyedto a deeper blue shade.

Fibers are spun from the same solutions either by dry spinning, or bywet spinning. The fibers are substantially freed from solvent and dried.After cold-drawing the dried fibers 600-900 per cent at 120-l45 C. andsubsequently heat-treating them at 150 C. for one hour, the fibers aregiven the same dyeing and washing treatment described above with thesame results as for the films, a light tint being acquired by theunmodified polyacrylonitrile fibers and a deep and dense color beinggiven to the copolymer fibers. The polymers of this example are alsosoluble in dimethyl forrnamide, dimethyl acetamide, tetramethyl urea,butyrolactone, ethylene carbonate, formyl morpholine, etc.

Example 11 Five parts of the copolymer fiber C of Example I is dyed to adeep green shade using the vat color dimethoxydibenzanthrone at 70 C. ina bath containing 0.5 part of dye, 0.25 part sodium hydroxide, 0.5 partsodium hydrosulfite and 100 parts of water (:1 bath-fiber ratio).

After the first 15 minutes of heating, 0.25 part of Glau- 4 Example 111The procedure of Example I is repeated for the polymerization of thefollowing monomer compositions:

N-tirn Acrylo- Vinyl Copolymer Soluble Polymer beta-eyanonitrile Ohlondeacrylamide m Parts Parts Parts 92 5 3 DMF, DMA, etc. 87 10 3 DMF, DMA,etc. 82 15 3 DMF. DMA, etc. 77 20 3 NOzMe. 57 40 3 NOzMe. 37 60 3Acetone.

Sometimes copolymers D and E, when dissolved in nitromethane may havegelled, partially dissolved particles known as fisheyes. In such cases,the solubility may be improved by the addition of small amounts ofmaterials which are good solvents for acrylonitrile polymers, such asbutyrolactone, ethylene carbonate, dimethyl foramide, dimethylacetamide, tetramethyl urea, etc. In addition, certain materials whichare relatively poor solvents for polyacrylonitrile, such as diethylforamide, diethyl acetamide, diethyl propionamide, etc., may be added toimprove the solubility. Also, when acetone solutions of copolymer Fcontain gelled particles, clarification of the solution may be effectedby the addition of nitromethane, diethyl foramide, diethyl acetamide,etc.

Dyeing tests of these copolymers show improvements in dyeingsusceptibility'similar to those of Example 1.

Example IV The procedure of Example I is repeated for the polymerizationof the following monomer compositions:

and di-methyl-styrenes, mono- Dyeing tests of these copolymers showimprovements in dye susceptibility similar to Example I. In place ofstyrene, various styrene derivatives may be used, such asalpha-methyl-styrene; nuclear-substituted chloro-styrenes, i. e.,ortho-, meta-, and para-chloro-styrenes, dichlorostyrenes, for example,the 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, and 3,5-di-chloro-styrenes,trichloro-styrenes; cyano-styrenes, such as ortho-, meta-, andpara-cyanostyrenes, dicyanostyrenes; nuclear-substituted alkyl-styrenes,such as monoand di-ethyl-styrenes, monoand di-isopropyl-styrenes;aryl-substituted styrenes, -i. e., para-phenyl-styrene, etc.;cycle-aliphaticsubstituted styrenes, such as para-cyclohexyl-styrene;fluoro-styrenes, such as ortho-, meta-, para-fiuoro-styrene,difluoro-styrenes, etc.; trifluoro-methyl-styrenes, such as ortho-,meta-, and para-trifluoromethyl-styrenes, di-(trifluoro-methyl)-styrenes, and various other styrenes or mixtures of anynumber of these with each other or with styrene.

Example V The procedure of Example I is repeated for the polymerlzationof the following monomer compositions:

. N-(2-quin0lyl) Acrylovinylidene w Polymer beta-cyano- LopolymerSoluble ll).

nitrile Chloride acrylamide Parts Parts Parts 85 5 10 DMF, DMA, etc. 6525 10 DMI", DMA, etc. 45 45 10 DMF, DMA, etc. 25 65 10 DMF, DMA, etc. 585 10 DMF, DMA, etc.

With the above vinylidene chloride copolymers and similar copolymershaving a total of acrylonitrile and vinylidene chloride of at least 85per cent in the polymer molecules, only the more active solvents, suchas butyrolactone, ethylene carbonate, N,N-dimethyl acetamide,N,N-dimethyl foramide, etc., can be used as solvents.

The above copolymers dye more readily and thoroughly than similarcopolymers containing no pyridyl-type amide.

Example VI The procedure of Example I is repeated for the polymerizationof the following monomer compositions:

The dyeing tests of the copolymer products show dye susceptibilitysimilar to the copolymers of Example I.

Instead of copolymerizing the amides of this invention directly with theacrylonitrile, the amides may first be copolymerized with part of theacrylonitrile or with another monomer and this independently preparedcopolymer used to modify polyacrylonitrile or acrylonitrile copolymers.These modifying-copolymers may be prepared substantially in accordancewith the procedure of Example I and thereafter placed in solution andadded to a solution of polyacrylonitrile, so that a compositionconsisting of suificient polymeric amide results and satisfactory dyeingis obtained. As examples, polymers D and E of Example I may be used asmodifiers for the unmodified homopolymers and copolymers ofacrylonitrile. For example, polymer E of Example I, which consists of 80parts of acrylonitrile and 20 parts of amide has excellent compatibilitywith homopolymers of acrylonitrile. The overall amounts of amiderequired to improve the dyeability generally corresponds to the amountsindicated above for copolymers in which the main body of theacrylonitrile polymers contain the amide copolymerized directly therein,that is, at least about 0.1 per cent and up to per cent or even per centor higher amide may be desirable in the ultimate polymer mixture. Thefollowing example is illustrative.

Example VII dimethyl formamide and added to a dimethyl formamide.

solution of polyacrylonitrile, containing per cent polymer, so that acomposition consisting of 90 parts of polyacrylonitrile and 10 parts ofthe pyridyl beta-cyano-acrylamide copolymer is obtained so as to give anultimate polymer composition of 98 parts acrylonitrile and 2 partsPyridyl amide. The solution is heated to 130 C., after which thesolution is filtered. Films and fibers prepared from this mixture aredyed in accordance with the process of Example I, and satisfactorilydyed, shaped articles are obtained. The unmodified polyacrylonitrilewithout the addition of the pyridyl beta-cyano-acrylamide copolymershows little or no dye retention.

In many cases, it is desirable to use amide-acrylonitrile copolymerswhich have even a higher ratio of the amide as, for example, to parts ofthe amide copoly-,

merized with acrylonitrile or'methacrylonitrile and even thesecopolymers of higher amide proportions have good compatibility withacrylonitrile polymers. In other cases, the copolymers of pyridyl amidesof beta-cyano-acrylic or beta-cyano-methacrylic acid with other monomersare,

satisfactory such as, for example, copolymers of styrene, vinylchloride, vinylidene chloride, alpha-methyl-styrene, etc.

When it is desired to modify an acrylonitrile copolymer such as thecopolymer of acrylonitrile and styrene or the copolymers ofacrylonitrile and other copolymerizable ethylenic compounds, it isusually desirable to use as modifiers copolymers containing the samestructural units as are present in the acrylonitrile copolymer. Thus asthere are present in the acrylonitrile copolymer, structural unitsderived from the acrylonitrile and styrene, it is desirable to havepresent in the modifying copolymer structural units derived from styrenein addition'to those derived from acrylonitrile and the amide. By thusincluding in the modifying copolymers structural units of stituted.

the same type as the structural units of the copolymer to be modified,greater compatibility between the acrylonitrile copolymer to be modifiedand the modifying copolymer is obtained and the two are more readilysoluble in the mutual solvent and will more readily mix into homogeneouspolymer mixtures.

The polymerization products of the present invention have in the polymermolecule a plurality of repeating units of the formula in which R, R,and P are substituents of the type indicated above and will containadditional repeating units of the formula when the amide iscopolymerized with acrylonitrile.

In addition, the polymerization products may contain any number ofrepeating units of the type obtained by the copolymerization of apyridyl amide of beta-cyanoacrylic or beta-cyano-methacrylic acid or amixture of acrylonitrile and the amide, with one or more copolymerizableethylenic compounds, such as, for example, vinylidene chloride, vinylchloride, styrene, alpha-methylstyrene, and methacrylonitrile. When thepolymerization mass contains, in addition to the pyridyl acrylic amidederivative, a polymerizable monomer having a CH2=C group in an amountsuch that the latter monomer is present to an extent of at least 50 moleper cent of the overall monomer content, then such monomers asfumaronitrile, beta-cyano-acrylamide and methyl betacyano-acrylate mayalso be present in the polymerization mixture.

As previously indicated, the solvent resistance of such copolymers thatcontain one or more monomer units in addition to those formed by theacrylonitrile and the N- pyridyl amide is affected by the type andproportion of copolymerizing monomer or monomers used to replace part ofthe acrylonitrile. For example, copolymers containing small amounts ofpyridyl amide units may contain various proportions of such monomerunits as obtained from vinylidene chloride, methacrylonitrile,fumaronitrile, and beta-cyanoacrylamide without considerable reductionin solvent resistance. Replacement of acrylonitrile units in thecopolymers by vinyl chloride, styrene and alpha-methyl-styrene unitsresult in copolymers of lowered solvent resistance, the amount of suchlowering in resistance in each case depending on the amount sub- Inaddition to the solvent resistance, certain other physical properties ofthe copolymers are affected by the presence of these additional units inthe copolymers. The amount and'character of the changes in physicalproperties of these copolymers depend again on the type and proportionof copolymerizing monomer or monomers used. For example, the tensilestrength of an acrylonitrile-N-pyridyl amide type copolymer willdecrease much more when a monomer having relatively Weak secondarybonding forces, such as styrene or ethylene is used to replace part ofthe acrylonitrile than when one or more monomers having relativelystrong bonding forces, such as methacrylonitrile, fumaronitrile,betacyano-acrylamide, methyl beta-cyano-acrylate and vinylidenechloride, is used to replace part of the acrylonitrile. Moreover, theability of these copolymers to form molecularly oriented shaped articlesdepends on the type and amount of the copolymerizing monomer or monomersused to replace acrylonitrile.

Other copolymerizable ethylenic compounds, which may also be present inthe polymerizable masses for copolymerization with the pyridyl amidesinclude one or more of the following: acrylates, e. g. methyl acrylate;

.methacrylates, e. g. methyl methacrylate; acrylamides;

In addition to the monomers, the polymerizable mass may also containother materials such as catalysts, e. g. peroxides, such as benzoylperoxide, naphthyl peroxides, phthalyl peroxide, tertiary-butylhydroperoxide, hydrogen peroxide, cyclohexyl hydroperoxide,tertiary-butyl perbenzoate, etc., azo catalysts, persulfates, such asammonium persulfate, etc., solvents, suspension or emulsion media,emulsifying agents, suspension agents, plasticizers, lubricants, etc.

For use in the preparation of shaped articles, the polymerizationproducts of this invention have molecular weights preferably of at leastabout 10,000. However, polymerization products of molecular weights lessthan 10,000 may be used for other purposes, such as impregnants, solventresistant coatings, etc. The molecular weight of the polymerizationproducts is dependent on the concentrations of the monomers, the amountand type of catalyst, the temperature of reaction, etc.

As is quite generally known in the field of high polymers, molecularorientation is usually indicated and identified by birefringence ofpolarized light, as under Nicol prisms, by increased density as comparedto the density of the same polymer unoriented, and by characteristicX-ray diifraction patterns. line or oriented, its X-ray diagram showsbright areas or spots for points of crystallization and dark areas forthe non-crystalline regions. The intensity or number of these brightspots increases with the degree of orientation or crystallization.Amorphous or non-crystalline materials give X-ray diagrams having veryfew high lights or bright spots whereas crystalline or orientedmaterials give definite X-ray diffraction patterns. In these patternsthere are definite relationships of the bright spots with regard toposition and spacing which are generally characteristic of thecomposition of the material being X-rayed. In fibers or films theorientation usually follows the direction of drawing or stretching sothat the orientation is parallel to the fiber axis or a major surface.

When a material is crystal- 7 Useful fibers may be made from thesolutions of the copolymers of this invention by dry spinning, as in thepreparation of cellulose acetate fibers, or by wet spinning, as in thepreparation of viscose rayon. In wet spinning, the solution of copolymermay be spun into a substance which is a non-solvent for the copolymer,but which is advantageously compatible with the solvent in which thecopolymer is dissolved. For example, water, acetone, methyl alcohol,carbon disulfide, glycerine, chloroform, carbon tetrachloride, benzene,etc., may be used as a precipitating bath for N,N-dimethyl acetamide,N,N,N,-;

N-tetramethyl urea, butyrolactone, ethylene carbonate,

and other solvent compositions of these copolymers. The extruded fibers,from which substantially all of the solvent has been removed in thespinning step, about 1-10 per per cent; and the drawn fiberheat-treated, usually at substantially constant length, at about 100-160C. to eifect further crystallization and removal of the remainingsolvent. the application of heat to an object, usually at a controlledtemperature and usually by means of the medium surrounding the object.

Many of the acrylonitrile copolymers of this invention may bemolecularly oriented, especially if there is no:

more than 15 per cent pyridyl amide of beta-cyano-acrylic orbeta-cyano-methacrylic acid in the polymer molecule. This is true whenthe major portion of the copolymer is acrylonitrile, for example, 85 percent or more acrylonitrile, or when the other copolymerizing monomersused in making such copolymers have substituent groups havingsecondary-valence bonding forces equal to or greater than exhibited bythe cyano group in acrylonitrile. For example, if such monomers asmethacrylonitrile, fumaronitrile, vinylidene chloride,beta-cyano-acrylamide and methyl beta-cyano-acrylate are used withacrylonitrile and the pyridyl amide, the proportion of acrylonitrile inthe copolymers may be much less than 85 per cent without destroying thecapacity for molecular orientation. Molecularly oriented, cold-drawn,shaped articles of particular usefulness are prepared from copolymercompositions containing in the polymer molecules -999 per centacrylonitrile, 0.1-15 per cent, advantageously 0.1beta-cyano-methacrylic acid, with or without one or more to 5 per cent,pyridyl amide of beta-cyano-acrylic or monomers of the class consistingof vinylidene chloride,

The term heat-treated, as used herein, refers to A cent remaining in theshaped article, may then be colddrawn about 100-900 per cent, preferablyabout 300-600 vinyl chloride, styrene, alpha-methyl-styrene,methacrylonitrile, fumaronitrile, beta-cyano-acrylamide and methylbeta-cyano-acrylate, the effects of the presence of the monomers of thisclass being noticeable when the monomer is present in the polymermolecule in amounts of one per cent or more.

The polymerization products of this invention show great afiinity forthe acetate, acidic, and vat dyes. The cellulose acetate dyes which areeffective with these copolymers are mainly amino-anthraquinonederivatives. A number of other acidic dyes that can be used areanthranilic acid 1-(4-sulfophenyl)-3-methyl 5 pyrazolone;1,5-diamino-4,8-dihydroxyanthraquinone-3-sulfonic acid;1-aminonaphthalene-4-sulfonic acidalphanaphthol- 4-sulfonic acid; thesodium salt of sulfanilic acidaniline- 2-benzoyl-amino 5 naphthol 7sulfonic acid; the sodium salt of 4,4 diaminostilbene 2,2 di sulfonicacid 3(phenol)2 ethylated; 1,5-diamino 4,8dihydroxyanthraquinone-B-sulfonic acid; dye prepared by diazotizing1-an1inonaphthalene-4-sulfonic acid and coupled withalpha-naphthol-4-sulfonic acid; the sodium salt of (m-aminobenzoicacido-anisidine) phosgenated; the sodium salt of(2-naphthol-6,8-disulfonic acid benzidine phenol) ethylated;dimethoxy-dibenzanthrone; andl,5-di-p-anisoylaminoi,8-dihydroxyanthraquinone.

From the molecularly orientable copolymers of this invention fibers maybe prepared having improved dyeing properties, low shrinkage in boilingwater, sometimes as low as 3 to 5 per cent or less of the cold-drawn orstretched article, good heat-resistance, and tensile strength in theorder of 4 to 6 grams per denier. Moreover, these properties make thefibers desirable in the manufacture of hosiery and for such all-purposefabrics as used for blouses, shirts, suits, etc.

What is claimed is:

1. The polymerization product having acid reactive groups obtained bypolymerizing a mass comprising an n-pyridyl amide of an acid selectedfrom the class consisting of beta-cyano-acrylic andbeta-cyano-methacrylic acids and a polymerizable monomer having a CH2=Cgroup in which the pyridyl group consists of one nitrogen atom, fromfive to ten carbon atoms, and hydrogen.

2. The composition of claim 1 in which the mass contains a polymerizableethylenic compound selected from the class consisting of acrylonitrile,vinyl chloride, vinylidene chloride, styrene, alpha-methyl-styrene,methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, and methylbeta-cyano-acrylate.

3. The polymerization product having acid reactive groups obtained bypolymerizing a mass comprising acrylonitrile and an n-pyridyl amide ofan acid selected from the class consisting of beta-cyano-acrylic andbetacyano-methacrylic acids in which the pyridyl group consists of onenitrogen atom, from five to ten carbon atoms, and hydrogen.

4. The copolymer of claim 3 in which the amide is present in at leastabout 0.1 per cent of the polymerizable mass.

5. A polymeric composition having in the polymer molecule a plurality ofrepeating acid reactive units having the formula OH2FCH 8. The polymericcomposition of claim 5 which contains the polymer molecule a pluralityof repeating units of the formula 9. A polymerization product havingacid reactive groups obtained by polymerizing a mass comprising an Npyr-idyl beta-cyano-acrylamide and a polymerizable monomer having a CH2=C group in which the pyridyl group consists of one nitrogen atom, fromfive to ten carbon atoms, and hydrogen.

10. A polymeric composition having in the polymer molecule a pluralityof repeating acid reactive unit-s having the formula in which P is thepyridine radical, said pyridine radical being attached to the amidonitrogen atom by a nuclear carbon atom.

11. The polymerization product of claim which contains in the polymermolecule a plurality of repeating units of the formula 12. A shapedarticle comprising a copolymer of acrylonitrile and N-pyridyl amide ofan acid selected from the class consisting of betacyanoacrylic andbeta-cyanomethacrylic acids in which the pyridyl group consists of onenitrogen atom, from five to ten carbon atoms, and hydrogen, saidcopolymer having repeating acid reactive groups and a molecular weightof at least 10,000.

13. A cold-drawn shaped article having molecular orientation and dyesusceptibility to acid dyes, said article comprising a copolymer ofacrylonitrile and an amide having the following formula in which R isselected from the class consisting of hydrogen and the methyl radical; Ris selected from the class consisting of hydrogen and alkyl groups and Pis an N-pyridyl group consisting of one nitrogen atom, from five to tencarbon atoms, and hydrogen, said copolymer having a molecular weight ofat least about 10,000 and containing in the polymer molecule no morethan about per cent by weight of the amide.

14. A cold-drawn shaped article having molecular orientation and dyesusceptibility to acid dyes, said article comprising a copolymer ofabout 60-989 per cent by weight acrylonitrile, about 0.1 to 5 per centby weight an amide having the following formula in which R is selectedfrom the class consisting of hydrogen and the methyl radical; R isselected from the class consisting of hydrogen and alkyl groups and P isan N-pyridyl group consisting of one nitrogen atom, from five to tencarbon atoms, and hydrogen and up to 39.9 per cent by weight of acompound selected from the class consisting of vinyl chloride,vinylidene chloride, styrene, alpha-methyl-styrene, methacrylonitrile,fumaronitrile, beta-cyano-acrylamide, and methyl beta-cyano-acrylate.

15. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer ofacrylonitrile and N-pyridyl amide of beta-cyano-acrylic acid, saidcopolymer having a mo- 'lecular weight of at least about 10,000 andcontaining in the polymer molecule no more than about 15 per cent byweight of said amide.

16. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer of about60-989 per cent by weight acrylonitrile, about 0.1 to 5 per cent byweight N-pyridyl betacyano-acrylamide, and about 1 to 39.9 per cent byweight of a compound selected from the class consisting of vinylchloride, vinylidene chloride, styrene, alpha-methylstyrene,methacrylonitrile, fumaronitrile, beta-cyanoacrylamide, and methylbeta-cyano-acrylate.

17. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer of about6098.9 per cent by weight acrylonitrile, about 0.1 to 5 per cent byweight N-pyridyl beta-cyano-acrylamide and about 1 to 39.9 per cent byweight vinylidene chloride.

18. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, and fiber comprising a copolymer of about60-989 percent by weight acrylonitrile, about 0.1 to 5 per cent byweight N-pyridyl beta-cyano-acrylamide and about 1 to 39.9 per cent byweight vinyl chloride.

19. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer of about60-989 per cent by weight acrylonitrile, about 0.1 to 5 per cent byweight N-pyridyl beta-cyano-acrylamide and about 1 to 39.9 per cent byweight styrene.

'20. A cold-drawn fiber having molecular orientation and dyesusceptibility to acid dyes, said fiber comprising a copolymer of about60-989 per cent by weight acryloni-trile, about 0.1 to 5 per cent byweight an amide having the following formula in which P is the pyridineradical, said pyridine radical being attached to the amido nitrogen atomby a nuclear carbon atom, and about 1 to 39.9 per cent by weight of acompound selected from the class consisting of vinyl chloride,vinylidene chloride, styrene, alpha-methylstyrene, methacrylonitrile,fumaronitrile, 'betaacyanoacrylamide and methyl beta-cyano-acrylate.

21. As a new monomeric composition of matter a compound having theformula in which R is selected from the class consisting of hydrogen andthe methyl radical; R is selected from the class consisting of hydrogenand alkyl groups and P is an N-pyridyl group consisting of one nitrogenatom, from five to ten carbon atoms, and hydrogen.

22. As a new monomeric composition of matter a compound having theformula in which P is the pyridine radical, said pyridine radical beingattached to the amido nitrogen atom by a nuclear carbon atom.

23. As a new monomeric composition, an N-pyridyl amide of an acidselected from the class consisting of beta-cyano-acrylic andbeta-cyano-methacrylic acid-s in which the pyridyl group consists of onenitrogen atom, from five to ten carbon atoms, and hydrogen.

24. As a new monomeric composition, an N-pyridyl beta-cyanoacrylamide inwhich the pyridyl group consists of one nitrogen atom, from five to tencarbon atoms, and hydrogen.

'25. As a new monomeric composition, an N-pyridylbeta-cyano-methacrylamide in which the pyridyl group consists of onenitrogen atom, from five to ten carbon atoms, and hydrogen.

26. As a new monomeric composition, N-(2-pyridyl) beta-cyano-acrylamide.

27. As a new monomeric composition, N-(2-pyridyl)beta-cyano-methacrylamide.

UNITED STATES PATENTS References Cited in the file of this patent2,508,860 Grimmel May 23, 1950 FOREIGN PATENTS 943,459 France 1948 OTHERREFERENCES g'laier: Das Pyridine und seine derivate, 1934, p.

1. THE POLYMERIZATION PRODUCT HAVING ACID REACTIVE GROUPS OBTAINED BYPOLYMERIZING A MASS COMPRISING AN N-PYRIDYL AMIDE OF AN ACID SELECTEDFROM THE CLASS CON SISTING OF BETA-CYANO-ACRYLIC ANDBETA-CYANO-METHACRYLIC ACIDS AND A POLYMERIZABLE MONOMER HAVING A CH2=C<GROUP IN WHICH THE PYRIDYL GROUP CONSISTS OF ONE NITROGEN ATOM. FROMFIVE TO TEN CARBON ATOMS, AND HYDROGEN.